CN106550606A - Kirsite method for plating - Google Patents
Kirsite method for plating Download PDFInfo
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- CN106550606A CN106550606A CN201580000922.5A CN201580000922A CN106550606A CN 106550606 A CN106550606 A CN 106550606A CN 201580000922 A CN201580000922 A CN 201580000922A CN 106550606 A CN106550606 A CN 106550606A
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- zinc alloy
- electroplating method
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Automation & Control Theory (AREA)
Abstract
The present invention provides a kind of Zinc alloy electroplating method, its be included in the Alkaline Zinc alloy electroplating bath for possess negative electrode and anode in the Zinc alloy electroplating method that is powered, it is characterized in that, cathode zone containing negative electrode and the anode region containing anode are mutually isolated by anion exchange membrane, the catholyte that cathode zone contains is alkaline zinc alloy bath, and the anolyte that anode region contains is alkaline aqueous solution.
Description
Technical field
The present invention relates to a kind of kirsite method for plating.Specifically, it is related to a kind of to steel beam column etc.
When implementing the excellent Alkaline Zinc alloy plated of anticorrosive property, by easy anode xegregating unit, energy
Enough sides maintain the method for plating for using the plating bath performance length of side phase.
Background technology
Kirsite plating has excellent corrosion resistance compared to zinc plating, therefore, it is widely used
In automobile component etc..Among kirsite plating, especially alkaline zinc-nickel alloy plating is applied to
Require the fuel part of highly corrosion resistant, the engine components being placed under hot environment.Alkali zinc nickel
Alloy plating bath is to dissolve nickel after selection is suitable to the amine system chelating agen of Ni eutectoid rates, makes zinc and nickel eutectoid
Plating bath on coating.But, when implementing alkaline zinc-nickel alloy plating, during energization near anode
The oxidation Decomposition of amine system chelating agen becomes problem.The oxidation Decomposition of amine system chelating agen is because in Anode
Into active oxygen caused by.In the case where the Ferrious material ion such as nickel ion, iron ion coexists,
These ions become oxidation catalyst, further promote the oxidation Decomposition of amine system chelating agen.Therefore,
When alkaline zinc-nickel alloy plating solution is with positive contact, amine system chelating agen fast decoupled so that plating
Can reduce.The accumulation of the analyte can produce current efficiency reduction, bath voltage rising, coating film thickness
Nickel containing ratio in reduction, coating reduces, is capable of the current density range diminution of plating, gloss drop
The problems such as low, COD risings.It is thus impossible to enough life-time service plating solutions, it is necessary to change plating solution.
It is as the method for improving the problems referred to above, known so far to there is several methods that.For example, in day
Following method is disclosed in Ben Tebiao 2002-521572 publications：With the sun being made up of (per) fluoropolymer
The anolyte of the catholyte and acidity of the alkaline zinc-nickel bath of ion exchange membrane isolation.But, by Acidic Liquid
In the case of anolyte, anode must be used and be plated with the high price corrosion-resistant member such as titanium of platinum.
In addition, when barrier film is damaged, it is also possible to which the alkalescence of the acid solution and cathode side of anode-side occurs
Dissolve the accident for being mutually mixed and producing violent chemical reaction.On the other hand, using alkalies generation
For Acidic Liquid as anolyte in the case of, because be powered cause anolyte acutely move to catholyte,
The liquid level of anolyte is reduced and the liquid level of catholyte rises generation simultaneously, and this is by the present inventor etc.
Plating run confirmed.
In Japanese Unexamined Patent Publication 2007-2274 publications, record as the method for solving foregoing problems and adopt
The method that supply alkaline components are added to basic anolyte with cation exchange membrane.But, the method
Additional equipment, liquid management etc. are needed, is operated miscellaneous.
In addition, in Japanese Unexamined Patent Application Publication 2008-539329 publication, disclosing cloudy by filter membrane isolation
Pole and the interelectrode zinc alloy coating bath of anode.But, the present inventor etc. is had found after confirming, open
Filter membrane can not prevent the movement of catholyte and anolyte, it is impossible to prevent the chelating agen at anode
Decomposition.Further, since zinc alloy bath in anolyte, is also used, therefore, promote very much anode
The decomposition of liquid.Accordingly, it would be desirable to change anolyte, in the case where being changed without, analyte is moved to
In the plating solution of negative electrode.Therefore recognize substantially without prolongation fluid life.
The content of the invention
The problem of the present invention is to provide a kind of method for plating, and the method economically can be realized simply
Anode isolation, and easy equipment is managed by liquid level, be able to maintain that zinc alloy coating bath performance and
Realize long lifetime.
The present invention is the invention completed based on following cognition：In the Alkaline Zinc for possessing negative electrode and anode
In alloy electroplating bath, by anion exchange membrane by the cathode zone containing negative electrode and containing anode
Anode region is mutually isolated, the catholyte contained as cathode zone using alkaline zinc alloy bath,
The anolyte contained as anode region using alkaline aqueous solution, carries out Zinc alloy electroplating, thus,
The anode region movements such as zinc ion in plating solution can not only be prevented, additionally it is possible to the amine in preventing from bathing
It is the movement of chelating agen anode region, does not produce oxidation Decomposition.In addition, it is thus understood that due to anode region
The electrolyte in domain is not also moved to cathode zone, and the liquid level of two Room does not change, therefore, liquid level pipe
Also there is no problem for reason.That is, the present invention provides a kind of Zinc alloy electroplating method, and which is to be included in tool
The Zinc alloy electroplating method being powered in the standby Alkaline Zinc alloy electroplating bath containing negative electrode and anode, which is special
Levy and be, the cathode zone containing negative electrode and the anode region containing anode pass through anion exchange membrane
Mutually isolated, the catholyte that cathode zone contains is alkaline zinc alloy bath, and anode region contains
Anolyte be alkaline aqueous solution.
According to the present invention, it is possible to provide one kind economically realizes the isolation of easy anode, and by liquid level
Manage easy equipment to be able to maintain that zinc alloy coating bath performance and realize the method for plating of long lifetime.
Description of the drawings
Fig. 1 represents the plating run result (plating outward appearance) of embodiment 1 and comparative example 1；
Fig. 2 represents the plating run result (coating film thickness distribution) of embodiment 1；
Fig. 3 represents the plating run result (coating film thickness distribution) of comparative example 1；
Fig. 4 represents the plating run result (distribution of Ni eutectoid rate) of embodiment 1；
Fig. 5 represents the plating run result (distribution of Ni eutectoid rate) of comparative example 1.
Specific embodiment
The method of the present invention is powered in being included in the Alkaline Zinc alloy electroplating bath for possessing negative electrode and anode
Zinc alloy electroplating method, wherein, the cathode zone containing negative electrode and the anode region containing anode
Mutually isolated by anion exchange membrane, the catholyte contained by cathode zone is alkaline zinc alloy bath,
The anolyte that anode region contains is alkaline aqueous solution.
As the metal combined with zinc with kirsite plating form, can enumerate be selected from nickel, ferrum,
Cobalt, stannum, more than one metal of manganese.Specifically, there are admiro plating, zinc-iron alloy
Plating, zinc-cobalt alloy plating, manganese alloy plating, Zinc-tin alloy plating, zinc-nickel cobalt alloy plating
Deng but be not restricted to that these alloy plateds.It is preferred that kirsite plating is admiro plating.
As anion exchange membrane, as long as the anion exchange membrane of effect of the present invention is played,
It is not particularly limited, wherein, preferably hydrocarbon system anion exchange membrane, particularly preferably hydrocarbon system quaternary ammonium
Base alkaline anion-exchange membrane.In addition, for its form it is not also specifically limited, can be ion
The film of exchanger resin itself, or make olefin-based etc. micro-porous film space in filled with the moon
The film of ion exchange resin or be micro-porous film and anion exchange membrane stacked film.
As the partition method using anion exchange membrane, it is not particularly limited, for example can be using such as
The known methods such as lower method：Organosilicon is used to being provided with the plastics of energization window, the anode chamber of ceramics
Filler etc. is arranged at film on window and fixed.
As anode, preferably enumerate ferrum, rustless steel, nickel, carbon etc., or platinum plating titanium,
Corrosion-resistant metal as palladium-tin alloy.
Negative electrode is the plated application for applying kirsite plating.As plated application, can enumerate ferrum, nickel,
The various metals such as copper and their alloy；Or implement the aluminum of zinc replacement Treatment etc. metal,
The variously-shaped materials such as the plate object of alloy, cuboid, cylinder, cylinder, sphere.
Alkaline zinc alloy bath used in the present invention contains zinc ion.The concentration of zinc ion is preferably
2～20g/L, more preferably 4～12g/L.As zinc ion source, Na can be enumerated2[Zn(OH)4]
、K2[Zn(OH)4], ZnO etc..These zinc ion sources can be used alone, or can also be by 2
Plant combination of the above to use.
In addition, the alkaline zinc alloy bath used in the present invention contain selected from nickel ion, iron ion,
The metal ion of more than a kind in cobalt ion, tin ion, manganese ion.Aforementioned metal ion it is total
Concentration is preferably 0.4～4g/L, more preferably 1～3g/L.As metal ion source, can enumerate
Nickel sulfate, ferrous sulfate, cobaltous sulfate, stannous sulfate, manganese sulfate etc..These metal ion sources can
To be used alone, or two or more can also be applied in combination.Alkaline Zinc used in the present invention
Alloy electroplating bath is preferably the alkaline zinc-nickel alloy plating solution containing nickel ion as aforementioned metal ion.
In addition, the alkaline zinc alloy bath used in the present invention preferably comprises caustic alkali.As causticity
Alkali, can enumerate sodium hydroxide, potassium hydroxide etc., preferably sodium hydroxide.The concentration of caustic alkali is excellent
Elect 60～200g/L, more preferably 100～160g/L as.
In addition, alkaline zinc alloy bath preferably comprises amine system chelating agen.As amine system chelating agen, can
Enumerate such as alkylidene amine compound such as ethylenediamine, trien, tetren, front
State ethylene oxide adduct, the propylene oxide adduct of alkylene amines；N- (2- amino-ethyls) ethanolamine,
The amino alcohols such as 2- Hydroxy-ethylamino propylamine；N-2 (- hydroxyethyl)-N, N ', N '-triethylethylenediamine,
N, N '-two (2- hydroxyethyls)-N, N '-diethyl ethylenediamine, N, N ', N ', N '-four (2- hydroxyethyls)
Propane diamine, N, N ', N ', poly- (hydroxy alkyl) alkylidene such as N '-four (2- hydroxypropyls) ethylenediamine two
Amine；By poly- (alkylene imine) of the acquisitions such as aziridine, 1,2- propyleneimines, by ethylenediamine,
Poly- (alkylene amines) of the acquisitions such as trien, ethanolamine, diethanolamine or poly- (amino
Alcohol) etc..These amine system chelating agen can be used alone, or can also make two or more combination
With.The concentration of amine system chelating agen is preferably 5～200g/L, more preferably 30～100g/L.
Alkaline zinc alloy bath used in the present invention can further contain selected from polishing material, put down
The material of more than a kind in the group of the auxiliary additives such as lubrication prescription and defoamer composition.The present invention
Used in alkaline zinc alloy bath preferably comprise polishing material.
As polishing material, as long as the known polishing material in the plating bath of zinc system, does not especially limit
System, for example, can enumerate：(1) polyoxyethylene polyoxypropylene block polymer, acetylenic glycols EO addition products
Etc. nonionic surfactants, polyoxyethylene laurel ether sulfate, alkyl diphenyl base ether disulfonic acid
The anion such as salt system surfactant；(2) diallyldimethylammonium chloride and sulfur dioxide are total to
The polyallylamine of polymers etc.；The condensation polymer of ethylenediamine and epoxychloropropane, dimethylamino propylamine and
The condensation polymer of epoxychloropropane, the condensation polymer of imidazoles and epoxychloropropane, 1- Methylimidazole .s, 2- methyl
The condensation polymer of the imdazole derivatives such as imidazoles and epoxychloropropane, containing methyl guanamines, benzoguanamine etc.
The poly- epoxypolyamine of the condensation polymer of heterocyclic amine and epoxychloropropane of pyrrolotriazine derivatives etc. etc.；3- dimethyl
The condensation polymer of aminopropyl carbamide and epoxychloropropane, double (N, N- dimethylaminopropyl) carbamide
Polyamine carbamide resin, N with the condensation polymer of epoxychloropropane etc., N- dimethylamino propylamines and alkylene
The polyamide polyamine of the water-soluble nylon resin of the condensation polymer of base dicarboxylic acids and epoxychloropropane etc. etc.；
The condensation polymer of diethylenetriamines, dimethylamino propylamine etc. and 2,2 '-Dichlorodiethyl ether, diformazan
The condensation polymer of base amino propylamine and 1,3- dichloropropanes, N, N, N ', N '-tetramethyl -1,3- diaminopropanes
Condensation polymer, N with 1,4- dichloroetane, N, N ', N '-tetramethyl -1,3- diaminopropanes and 1,3- dichloros
The polyalkylene polyamine of the condensation polymer of propane -2- alcohol etc.；Deng polyamino compound class；(3) dimethylamine
Deng the condensation polymer with dichloroether；(4) the aromatic series aldehydes such as 3,4-dimethoxybenzenecarbonal, vanillin, anisaldehyde,
Benzoic acid or its salt；(5) hexadecyltrimethylammonium chloride, 3- carbamoyl benzyl chlorides, pyridine
Deng quaternary ammonium salt etc..Wherein, preferably quaternary ammonium salt and aromatic series aldehydes.These polishing materials can be with
It is used alone, or two or more can also be applied in combination.For the concentration of polishing material,
In the case of aromatic series aldehydes, benzoic acid or its salt, preferably 1～500mg/L, further preferably
For 5～100mg/L, in the other cases, preferably 0.01～10g/L, more preferably
0.02～5g/L.
Additionally, it is preferred that the alkaline zinc alloy bath used in the present invention contains nitrogen heterocyclic ring quaternary ammonium salt light
Damp agent.Aforementioned nitrogen heterocyclic ring quaternary ammonium salt polishing material is more preferably the nitrogen-containing hetero that carboxyl and/or hydroxyl replace
Ring quaternary ammonium salt.As the nitrogen heterocyclic ring of aforementioned nitrogen heterocyclic ring quaternary ammonium salt, can enumerate such as pyridine ring,
Piperidine ring, imidazole ring, imidazoline ring, pyrrolidine ring, pyrazole ring, quinoline ring, morpholine ring etc.,
Preferably pyridine ring, the particularly preferably quaternary ammonium salt of nicotinic acid or derivatives thereof.Aforementioned quaternary ammonium salt chemical combination
In thing, carboxyl and/or hydroxyl for example can be replaced in nitrogen heterocyclic ring via substituent group as carboxymethyl
On.In addition, aforementioned nitrogen heterocyclic ring is in addition to carboxyl and/or hydroxyl, such as alkyl can also be contained
Etc. substituent group.As long as in addition, without prejudice to contains the effect of polishing material, forming heterocyclic quaternary ammonium cation
N substituent groups be not particularly limited, such as replacement, non-substituted alkyl, aryl, alkane can be enumerated
Epoxide etc..In addition, as the balance anion of forming salt, can enumerate for example containing halogenide it is cloudy from
Son, oxo-anions, borate anion, sulfonate anionic, phosphate anion, acyl are sub-
The compound of amine anion etc., preferably halide anions.Such quaternary ammonium salt is same in intramolecular
Shi Hanyou quaternary ammonium cations and oxo-anions, therefore the feature as anion is also showed that, because
This is preferred.As the specific example of nitrogen heterocyclic ring quarternary ammonium salt compound, such as N- benzyls -3- can be enumerated
Carboxyl pyridine chloride, N- styryl -4- carboxyl pyridine chlorides, N- butyl -3- carboxyl pyrroles
Pyridine bromide, N- chloromethyl -3- carboxyl pyridine bromides, N- hexyl -6- hydroxyl -3- carboxyl pyridines
Chloride, N- hexyl -6-3- hydroxypropyl -3- carboxyl pyridine chlorides, N-2- ethoxy -6- methoxies
Base -3- carboxyl pyridine chlorides, N- methoxyl group -6- methyl -3- carboxyl pyridine chlorides, N- propyl group
- 2- methyl -6- phenyl -3- carboxyl pyridine chlorides, N- propyl group -2- methyl -6- phenyl -3- carboxyl pyridines
Chloride, N- benzyl -3- carboxymethyl group pyridinium chlorides, 1- butyl -3- methyl -4- carboxyl imidazoles
Bromide, 1- butyl -3- methyl -4- carboxymethyl group imidazolium bromides, 1- butyl-2-hydroxy methyl
- 3- methylimidazolium chlorides, 1- butyl -1- methyl -3- methyl carboxyl pyridine chlorides, 1- butyl
- 1- methyl -4- methyl carboxyl piperazine heavy stone used as an anchor chlorides etc..These nitrogen heterocyclic ring quaternary ammonium salts can be used alone,
Or two or more can also be applied in combination.The concentration of nitrogen heterocyclic ring quaternary ammonium salt is preferably
0.01～10g/L, more preferably 0.02～5g/L.
As auxiliary additive, such as organic acid, silicate, sulfhydryl compound etc. can be enumerated.
These auxiliary additives can be used alone, or can also be applied in combination two or more.Auxiliary
The concentration of additive is preferably 0.01～50g/L.
As defoamer, such as surfactant etc. can be enumerated.These defoamer can be used alone,
Or two or more can also be applied in combination.The concentration of defoamer is preferably 0.01～5g/L.
As the alkaline aqueous solution used in the present invention, can enumerate for example containing selected from caustic alkali,
In the group of the sodium salt, potassium salt and ammonium salt and tetraalkylphosphonium hydroxide quaternary ammonium composition of mineral acid 1
Plant the aqueous solution of the above.As caustic alkali, sodium hydroxide, potassium hydroxide etc. can be enumerated.As nothing
Machine acid, can enumerate sulphuric acid etc..As tetraalkyl (alkyl of preferred carbon number 1～4) hydroxide
Quaternary ammonium, can enumerate such as tetramethyl quaternary ammonium hydroxide etc..It is containing caustic alkali in alkaline aqueous solution
In the case of aqueous solution, the concentration of caustic alkali is preferably 0.5～8mol/L, more preferably
2.5～6.5mol/L.In the aqueous solution that alkaline aqueous solution is the sodium salt comprising mineral acid, potassium salt or ammonium
In the case of, the concentration of inorganic acid salt is preferably 0.1～1mol/L, more preferably
0.2～0.5mol/L.In the case where alkaline aqueous solution is the aqueous solution containing tetraalkylphosphonium hydroxide quaternary ammonium,
The concentration of tetraalkylphosphonium hydroxide quaternary ammonium is preferably 0.5～6mol/L, more preferably 1.5～3.5mol/L.
Alkaline aqueous solution is preferably the aqueous solution containing caustic alkali, more preferably containing the water-soluble of sodium hydroxide
Liquid.
Temperature when implementing kirsite plating is preferably 15 DEG C～40 DEG C, more preferably 25～35 DEG C.
Cathode-current density when implementing kirsite plating is preferably 0.1～20A/dm2, more preferably
0.2～10A/dm2。
Then, by embodiment and comparative example, the present invention will be described, but the present invention is not limited
In these embodiments and comparative example.
Embodiment
(embodiment 1)
By anion exchange membrane SELEMION (Asahi Glass is manufactured, hydrocarbon system quaternary ammonium group alkalescence it is cloudy from
Proton exchange) isolate negative electrode and anode, alkalescence as follows is adopted as the catholyte of cathode chamber
Admiro plating solution (500mL), adopts 130g/L (3.3mol/L) as the anolyte of anode chamber
Sodium hydrate aqueous solution (50mL), by 400Ah/L be powered obtain admiro plating.It is cloudy
Electrode current density is 4A/dm2, anodic current density is 16A/dm2, plating bath is 25 DEG C.Plating
25 DEG C are maintained after liquid cooling.Negative electrode adopts iron plate, anode to adopt nickel plate.It should be noted that every
Energization 16Ah/L just changes the iron plate of negative electrode.The zinc ion concentration of catholyte is by impregnating dissolving metal
Zinc is remaining constant.Nickel ion concentration by feed the nickel sulfate hexahydrate compound containing 25wt% and
The aqueous solution of the IZ-250YB of 10wt% is remaining constant.The sodium hydroxide of catholyte and anolyte is dense
Degree periodic analysises, feed to which so that concentration remains constant.Polishing material is respectively according to recharge rate
The mode of 15mL/kAh and 15mL/kAh feeds the IZ-250YR1 (DIPSOL manufactures) of polyamine system
And the IZ-250YR2 (DIPSOL manufactures) of nitrogen heterocyclic ring quaternary ammonium salt system, carry out plating.Amine system
Chelating agen IZ-250YB is fed according to the mode of the recharge rate 80mL/kAh of IZ-250YB, is carried out
Plating.Often energization 200Ah/L just analyzes amine system chelating agent concentrations and concentration of sodium carbonate in catholyte.
In addition, adopting the long battery (long cell) using the iron plate of 20cm as negative electrode, tried based on Hull groove
Testing carries out plating run, determines the distribution of plating outward appearance, film thickness distribution and Ni eutectoid rate.Need
It is bright, plating run condition be 4A-20 minutes, 25 DEG C.
Plating solution is constituted：
(Zn ion sources are Na to Zn ion concentrations 8g/L2[Zn(OH)4])
Ni ion concentrations 1.6g/L (Ni ion source NiSO4·6H2O)
Naoh concentration 130g/L
Amine system chelating agen (the oxa- cycloalkanes addition products of alkylene amines) IZ-250YB (DIPSOL
Company manufactures) 60g/L
Polishing material IZ-250YR1 (manufacture of DIPSOL companies) 0.6mL/L (polyamine 0.1g/L)
Polishing material IZ-250YR2 (manufacture of the DIPSOL companies) 0.5mL/L (quaternary ammonium salts of nicotinic acid
0.2g/L)
(comparative example 1)
Do not isolate negative electrode and anode, using alkaline zinc-nickel alloy plating solution (500mL) as follows,
It is powered by 400Ah/L and obtains admiro plating.Cathode-current density is 4A/dm2, anode electricity
Current density is 16A/dm2, plating bath is 25 DEG C.25 DEG C are maintained after plating solution cooling.Negative electrode is adopted
Iron plate, anode adopt nickel plate.It should be noted that often energization 16Ah/L just changes the iron plate of negative electrode.
Zinc ion concentration remains constant by impregnating dissolving metallic zinc.Nickel ion concentration is contained by supply
The aqueous solution of the IZ-250YB of the nickel sulfate hexahydrate compound and 10wt% of 25wt% is remaining constant.Hydrogen
Oxidation na concn periodic analysises, feed to which so that concentration remains constant.Polishing material is respectively according to benefit
IZ-250YR1 (the DIPSOL of polyamine system are fed to the mode of rate 15mL/kAh and 15mL/kAh
Manufacture) and nitrogen heterocyclic ring quaternary ammonium salt system IZ-250YR2 (DIPSOL manufactures), carry out plating.
Amine system chelating agen IZ-250YB is fed according to the mode of the recharge rate 80mL/kAh of IZ-250YB,
Carry out plating.Often energization 200Ah/L just analyzes amine system chelating agent concentrations and concentration of sodium carbonate.In addition,
The long battery using the iron plate of 20cm as negative electrode is adopted, plating run is carried out based on hull trough test,
Determine the distribution of plating outward appearance, film thickness distribution and Ni eutectoid rate.It should be noted that plating run
Condition be 4A-20 minutes, 25 DEG C.
Plating solution is constituted：
(Zn ion sources are Na to Zn ion concentrations 8g/L2[Zn(OH)4])
Ni ion concentrations 1.6g/L (Ni ion source NiSO4·6H2O)
Naoh concentration 130g/L
Amine system chelating agen IZ-250YB (manufacture of DIPSOL companies) 60g/L
Polishing material IZ-250YR1 (manufacture of DIPSOL companies) 0.6mL/L
Polishing material IZ-250YR2 (manufacture of DIPSOL companies) 0.5mL/L
1 amine system chelating agent concentrations of table and concentration of sodium carbonate change
Embodiment 1 can be seen that following effect compared with comparative example 1.
(1) decomposition of amine system chelating agen is suppressed.
(2) accumulation of sodium carbonate is also suppressed.
(3) deterioration of plating outward appearance is suppressed.
(4) reduction of plating speed is suppressed.
(5) reduction of the Ni eutectoid rates in low current portion is suppressed.
By means of the invention it is possible to realize alkaline zinc alloy bath, especially alkaline zinc-nickel alloy plating solution
Long lifetime.In addition, by the length of alkaline zinc alloy bath, especially alkaline zinc-nickel alloy plating solution
In the life-span, can realize that the stabilisation of plating quality, the shortening of plating time, drainage sunk well are born
The mitigation of load.
Claims (10)
1. a kind of Zinc alloy electroplating method, which is to be included in the alkaline kirsite for possessing negative electrode and anode
The Zinc alloy electroplating method being powered in electroplating bath, it is characterised in that the cathode zone containing negative electrode and
Anode region containing anode is mutually isolated by anion exchange membrane, the catholyte that cathode zone contains
It is alkaline zinc alloy bath, the anolyte that anode region contains is alkaline aqueous solution.
2. Zinc alloy electroplating method according to claim 1, wherein, anion exchange membrane is
Hydrocarbon system anion exchange membrane.
3. Zinc alloy electroplating method according to claim 1 and 2, wherein, alkaline aqueous solution
It is comprising selected from caustic alkali, the sodium salt of mineral acid, potassium salt and ammonium salt and quaternary ammonium hydroxide
The aqueous solution of more than a kind in the group of composition.
4. the Zinc alloy electroplating method according to any one of claims 1 to 3, wherein, alkalescence
Aqueous solution is caustic-alkali aqueous solution, scope of its concentration in 0.5～8mol/L.
5. the Zinc alloy electroplating method according to any one of Claims 1 to 4, wherein, alkalescence
Zinc alloy bath contains zinc ion, metal ion, caustic alkali and amine system chelating agen, metal from
Son is selected from more than a kind of nickel ion, iron ion, cobalt ion, tin ion and manganese ion
Metal ion.
6. Zinc alloy electroplating method according to claim 5, wherein, amine system chelating agen contains
In the group constituted selected from the oxa- cycloalkanes addition product of alkylidene amine compound and alkylidene amine compound
More than a kind.
7. the Zinc alloy electroplating method according to claim 5 or 6, wherein, alkaline kirsite
Plating solution is further containing a kind in the group selected from polishing material, auxiliary additive and defoamer composition
More than.
8. Zinc alloy electroplating method according to claim 7, wherein, alkaline zinc alloy bath
Containing polishing material, polishing material contain selected from quaternary ammonium salt and aromatic aldehyde composition group in a kind with
On.
9. the Zinc alloy electroplating method according to any one of claim 1～8, wherein, alkalescence
Zinc alloy bath is alkaline zinc-nickel alloy plating solution.
10. the Zinc alloy electroplating method according to any one of claim 1～9, wherein, anode
Selected from the group of ferrum, rustless steel, nickel and carbon composition.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2015/070876 WO2016075963A1 (en) | 2015-07-22 | 2015-07-22 | Zinc alloy plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106550606A true CN106550606A (en) | 2017-03-29 |
| CN106550606B CN106550606B (en) | 2019-04-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580000922.5A Active CN106550606B (en) | 2015-07-22 | 2015-07-22 | Kirsite method for plating |
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| Country | Link |
|---|---|
| US (1) | US10156020B2 (en) |
| EP (1) | EP3042985B1 (en) |
| JP (1) | JP5830203B1 (en) |
| KR (1) | KR101622527B1 (en) |
| CN (1) | CN106550606B (en) |
| BR (1) | BR112015028630A2 (en) |
| MX (1) | MX368366B (en) |
| PH (1) | PH12015502422A1 (en) |
| RU (1) | RU2610183C1 (en) |
| TW (1) | TWI636164B (en) |
| WO (1) | WO2016075963A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110462107A (en) * | 2019-02-15 | 2019-11-15 | 迪普索股份公司 | Zinc or Zinc alloy electroplating method and system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3559318A1 (en) * | 2016-12-22 | 2019-10-30 | Carl Freudenberg KG | Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods |
| KR101847439B1 (en) * | 2017-07-25 | 2018-04-10 | 기양금속공업(주) | Direct zinc electroplating method on aluminium or aluminium alloys |
| PL3461933T3 (en) * | 2017-09-28 | 2020-03-31 | Atotech Deutschland Gmbh | Method for electrolytically depositing a zinc-nickel alloy layer on at least a substrate to be treated |
| KR101854195B1 (en) * | 2017-10-13 | 2018-05-04 | 배명직 | Process for Diect Zinc electroplating of Aluminum alloys |
| RU2712582C1 (en) * | 2019-07-16 | 2020-01-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Electrolyte for electrodeposition of zinc-iron coatings |
| RU2711317C1 (en) * | 2019-09-25 | 2020-01-16 | Общество с ограниченной ответственностью "Инжиниринговый химико-технологический центр" (ООО "ИХТЦ") | Fast and scalable method of producing microporous 2-methylimidazolate of cobalt (ii) |
| US11661666B2 (en) * | 2019-10-10 | 2023-05-30 | The Boeing Company | Electrodeposited zinc and iron coatings for corrosion resistance |
| RU2720269C1 (en) * | 2019-11-12 | 2020-04-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method of producing corrosion-resistant electrochemical zinc-nickel-cobalt coating |
| CN111501071A (en) * | 2020-05-26 | 2020-08-07 | 珠海冠宇电池股份有限公司 | Nickel electrodeposition layer and workpiece comprising same |
| WO2022145170A1 (en) | 2020-12-28 | 2022-07-07 | ディップソール株式会社 | Method and system for electroplating article with metal |
| WO2023100381A1 (en) | 2021-12-02 | 2023-06-08 | ディップソール株式会社 | Method and system for electroplating article with metal |
| JP7233793B1 (en) | 2021-12-02 | 2023-03-07 | ディップソール株式会社 | Method and system for electroplating articles with metal |
| JP7442866B1 (en) * | 2022-11-25 | 2024-03-05 | ディップソール株式会社 | Electroplating anodes and methods and systems for electroplating articles with metals |
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2015
- 2015-07-22 MX MX2015014806A patent/MX368366B/en active IP Right Grant
- 2015-07-22 CN CN201580000922.5A patent/CN106550606B/en active Active
- 2015-07-22 JP JP2015537053A patent/JP5830203B1/en active Active
- 2015-07-22 US US14/782,671 patent/US10156020B2/en active Active
- 2015-07-22 EP EP15771005.4A patent/EP3042985B1/en active Active
- 2015-07-22 BR BR112015028630A patent/BR112015028630A2/en not_active IP Right Cessation
- 2015-07-22 RU RU2015142653A patent/RU2610183C1/en not_active IP Right Cessation
- 2015-07-22 WO PCT/JP2015/070876 patent/WO2016075963A1/en active Application Filing
- 2015-07-22 KR KR1020157030879A patent/KR101622527B1/en active IP Right Grant
- 2015-08-12 TW TW104126224A patent/TWI636164B/en active
- 2015-10-21 PH PH12015502422A patent/PH12015502422A1/en unknown
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| US6755960B1 (en) * | 2000-06-15 | 2004-06-29 | Taskem Inc. | Zinc-nickel electroplating |
| CN1922343A (en) * | 2004-02-26 | 2007-02-28 | 爱托特奇德国股份有限公司 | Baths, systems and processes for electroplating zinc-nickel ternary and higher alloys and articles so electroplated |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110462107A (en) * | 2019-02-15 | 2019-11-15 | 迪普索股份公司 | Zinc or Zinc alloy electroplating method and system |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112015028630A2 (en) | 2017-07-25 |
| MX368366B (en) | 2019-09-30 |
| EP3042985B1 (en) | 2019-04-10 |
| JP5830203B1 (en) | 2015-12-09 |
| TW201704548A (en) | 2017-02-01 |
| EP3042985A1 (en) | 2016-07-13 |
| TWI636164B (en) | 2018-09-21 |
| US10156020B2 (en) | 2018-12-18 |
| JPWO2016075963A1 (en) | 2017-04-27 |
| PH12015502422B1 (en) | 2016-02-22 |
| KR101622527B1 (en) | 2016-05-18 |
| US20170022621A1 (en) | 2017-01-26 |
| WO2016075963A1 (en) | 2016-05-19 |
| CN106550606B (en) | 2019-04-26 |
| MX2015014806A (en) | 2017-04-11 |
| EP3042985A4 (en) | 2016-08-17 |
| RU2610183C1 (en) | 2017-02-08 |
| PH12015502422A1 (en) | 2016-02-22 |
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